Neutralization of friedel-crafts catalyst



NEUTRALIZATION F FRIEDEL-CRAFTS CATALYST Helmuth G. Schneider, Westfield, N. J., and William C. Van Siclen, Brea, Califi, assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Application December 27, 1955, Serial No. 555,262

4 Claims. (Cl. 260-943) V This invention relates to an improved method for the destruction of catalyst residues and relates more particularly to the destruction of residues of Friedel-Crafts cata' lysts, such as aluminum chloride, used in the polymerization of various types of unsaturated hydrocarbons and is a continuation-in-part of application Serial No. 316,556, filed October 23, 1952.

Many types of hydrocarbon polymerizations employ metal halides of the Friedel-Crafts type as catalysts. Among these polymerizations is the polymerization of isoolefins, such as isobutylene, to solid rubbery polymers. Aluminum chloride is the most generally used of the Friedel-Crafts catalysts, but aluminum bromide, titanium tetrachloride and zirconium tetrachloride are used also. At the end of the reaction the catalyst must be destroyed to prevent further polymerization.

At the end of the reaction the product must be treated to destroy residual catalyst and to prevent the product from going otf color. It is known that a good proportion of the catalyst is actually bound up with the polymer, i. c. it terminates the polymer chain. If this catalyst is not released from the polymer and destroyed the resulting product is so color unstable as to be unmarketable. Various materials have been used for this purpose. For ex-' ample, alcohols, such as methanol and ethanol and alkalis such as sodium hydroxide can be used. Sodium hydroxide is used because of its convenience, ready availability, and cheapness. However, it has been considered necessary to use a large excess of the caustic in order to completely eliminate the catalyst. This in turn requires further washing to remove the excess caustic from the polymer. This excessive washing results in the formation of emulsions which are difficult to break. Furthermore the use of strong caustic causes the resulting polymer to lose color stability.

The present invention provides an improved process for the polymerization of polymerizable organic compounds catalyzed by a metallic halide and the like. It provides an improved process particularly applicable to the polymerization of an isoolenfin wherein the process can be carried out without the above difficulties.

It is therefore the major object of the present invention to provide a method for effectively destroying the catalyst used in the polymerization of isoolefins.

In accordance with this invention, this and other objects of the invention are accomplished by adding 0.5 to 3 volumes of aqueous caustic having a concentration between 0.1 and 1.0 wt. percent and containing to 100% molar excess of sodium hydroxide to the reactor contents and allowing the mixture to stand at a temperature between 20 and 65 C. preferably 50' and 65 C., for a time sufficient to complete the reaction between the caustic and aluminum chloride or other metal halide. The use of this amount of caustic in this strength results in the use of less caustic, increases the speed of settling, prevents the formation of emulsions, results in minimum solid aluminum hydroxide formation, and gives a polymer of good color stability.

The invention is particularly adapted to processes for nitecl States Patent 0 2,786,828 Patented Mar. 26, 1957 the polymerization of solid polymers from isobutylene or a hydrocarbon fraction containing it by contacting the isobutylene, preferably in a diluent such as hexane, with finely divided solid aluminum chloride or a slurry thereof in hexane at a temperature between and +40 C. at a velocity of about five feet per second. The polymer as it forms dissolves in the large excess of hexane present in the reactor and is withdrawn as a slurry with aluminum chloride. The slurry is cotnacted in an orifice mixer at a temperature of 20-65 C., preferably 5065 C. with an equal volume of caustic solution containing the desired molar excess of caustic between 10 and Under these conditions the amount of aluminum hydroxide precipitated is at a minimum. The mixture is allowed to settle into two layers, an upper layer consisting ofja solution of polymer in hexane and a lower layer of dilutecaustic containing most of the aluminum as a soluble sodium aluminate. These layers are separated and the caustic layer sent-to the sewer. It is particularly important that the pH of the aqueous layer be maintained between 9.5 and 12.5 in order to secure the complete elimini nation of the catalyst from the polymer.

While the invention has specific practical application to Example I A mixture of 30% isobutylene and 70% hexane .was

polymerized at -40 C. in the presence of finely divided aluminum chloride to give a solution of 20% polyisobutylene 'in hexane slurried with 0.3 wt. percent alumi num amends." "Different portions of the reactor efiluent were washed at 65 C. with diflerent volumes of dilute caustic and separately settled. The following data were obtained:

I Percent A] pH Aqueas insoluble ous Layer AI(OH):,

percent Mol. Ratio NaOH/A1018 s a-9: MQUICD tan- 00m Example II Other portions of the reactor contents of Example I were washed with equal volumes of caustic in which the molar excess of caustic over the aluminum chloride varied from 0 to 100%. The following data were obtained:

Percent Molar excess otNaOH ovcr A1013. 0 33.3 66.7 100 Percent of aluminum salts as insoluble ARCH); 97.5 4.8 6.1 7.5

From the above data it is evident that as the excess sodium hydroxide approaches zero the insoluble aluminum hydroxide increases rapidly but from 33% to 100% excess the amount of Al(OH)a precipitated is very small.

adapts, Polyisobutylene stripes-area as in eisiripl'r except that the process was carriediout continuously. The solution of polymer in hexane was continuously washedwith.

an equal volume of caustic containing 10% molar excess ofsoditunhydroxide over aluminumchloride and the mix-. ture' settled. The washedpolymer, was' stripped of hexane and the hexane recycled to the reactor. From 93 to 98% of.the aluminum salts were found in the aqueous phase by the continuous settling operation.

Example IV In a continuous process similar to Example III with equalvolume of caustic containing 100% molar excess the settling temperaturewas varied between 50 C. and 65" ,Ai1alysis.of the hydrocarbon phase, aqueous interfaceand aqueous phase for. aluminum content was made to indicate thedegree of separation. This is shown in the following table:

V Wt. percent Al on total Al added se ttlirig 'lemiiersture Hydroczm: Aqueous Aqueous bon Phase Interface base 7 Example V azii oh a a.t3qlo 1 tot Volume CaustioWash 'zi Initial s .16 4. .32 .40.

0% excess NaOII 9+ 9+ 9+ 7% 5 5% 250% excess NaOH. 9+ 9+ 9+ 7% 4% 4 1,250% excess NaOH 9+ 9+ 9+ 6' 3% 3% From the above examples it is clear that the aluminum chloride catalyst should be". washed from" the polymer solution by means of an equal volume of caustic containing between 10 and 100 mol'percent excess of sodium hydroxide at a temperature of 65 C.

The nature and objectsj'ofthepresent invention having been thus described and illustrated, wh at is claimed as new and useful and desired to be secured by Letters Patent is:

.1. In a process for'destnoying? residual catalyst in polymerization of isoolefins with nietal ha'lide catalysts by the addition of caustic" to the reaction mixture containing residual catalyst, the improvement which comprises maintaining the reaction mixture: ata pH between 9.5 and 12.5 by employing at least 0.510 3 volumes of dilute caustic per volume of reaction mixture; said caustic having a concentration between 0.1 and 1.0 wt. percent and containing between 10 and 100 mol percent excess of sodium hydroxide over that theoretically necessary to react with the catalyst. s

2. Process according to claim 1 in which the catalyst is aluminumchloride.

3. Process according. to. claim 2' in which the temperatureis'be'tween and C.

4. Process. for preparing polyisobut'ylene which comprises contacting a mixtureof 30% is'obutylene and hexane at 40 C. in thepr es'ence' of finely divided aluminum chloride whereby a slurry of polymer in reaction liquor is formed, maintaining the slurry at a pH between 9.5 and 12.5 by washing the reactor effluent at 20 120 C. with at least 0.5 to 3 volumes of dilute caustic per volume of reaction pnodu'ct said caustic having a concentration between 0.1 and 1.0 wt. percent and containing between 10 and mol percent excess sodium hydroxide over that theoretically necessary to react with the catalyst.

No references cited. 

1. IN A PROCESS FOR DESTROYING RESIDUAL CATALYST IN POLYMERIZATION OF ISOOLEFINS WITH METAL HALIDE CATALYST BY THE ADDITION OF CAUSTIC TO THE REACTION MIXTURE CONTAINING RESIDUAL CATALYST, THE IMPROVEMENT WHICH COMPRISES MAINTAINING THE REACTION MIXTURE AT A PH BETWEEN 9.5 AND 12.5 BY EMPLOYING AT LEAST 0.5 TO 3 VOLUMES OF DILUTE CAUSTIC PER VOLUME OF REACTION MIXTURE, SAID CAUSTIC HAVING A CONCENTRATION BETWEEN 0.1 AND 1.0 WT. PERCENT AND CONTAINING BETWEEN 10 AND 100 MOL PERCENT EXCESS OF SODIUM HYDROXODE OVER THAT THEORETICALLY NECESSARY TO REACT WITH THE CATALYST. 